A new type of nickel and palladium complexes with non-innocent β-diketiminate ligand having redox active phenol groups, 2,4-di-tert-butyl-6-(((1E,2E)-3-((3,5-di-tert-butyl-2-hydroxyphenyl) amino)-2-nitroallylidene)amino)phenol (LH3, fully protonated form) have been developed, and the structure, physical properties, and reactivity of their one-electron and two-electron oxidized complexes, [MII(L•2-)] and [MII(L-)]+ (M = NiII or PdII) have been examined in detail. The two-electron oxidized forms of both complexes, [MII(L-)]+, exhibited hydrogen atom abstraction ability from 1,4-cyclohexadiene (CHD) comparable to its copper analog [CuII(L-)]+ (Dalton Trans. 2013; 42: 2438-2444). The oneelectron oxidized form of palladium complex, [PdII(L•2-)], was also found to oxidize CHD, whereas the nickel analog, [NiII(L•2-)], exhibited photo-induced oxidation ability of CHD.
Bibliographical noteFunding Information:
This work was supported by a Grant-in-Aid for Scientific Research on Innovative Areas “Molecular Activation Directed toward Straightforward Synthesis” (No. 22105007) and “Stimuli-responsive Chemical Species” (No. 24109015) and a Grant-in-Aid for Exploratory Research (No. 25620044) from the Ministry of Education, Culture, Sports, Science and Technology, Japan. Y.M., N.F., and S.I. also express their special thanks to the JSPS Japanese-German Graduate Externship Program on “Environmentally Benign Bio-and Chemical Processes” for financial support of the stay in RWTH Aachen.
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- b-diketiminate ligand
- nickel complex
- non-innocent ligand
- palladium complex